CN106299213B - A kind of bacteria cellulose-base microporous compound film and its preparation method and application - Google Patents
A kind of bacteria cellulose-base microporous compound film and its preparation method and application Download PDFInfo
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- CN106299213B CN106299213B CN201510272604.6A CN201510272604A CN106299213B CN 106299213 B CN106299213 B CN 106299213B CN 201510272604 A CN201510272604 A CN 201510272604A CN 106299213 B CN106299213 B CN 106299213B
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- 241000894006 Bacteria Species 0.000 title claims abstract description 61
- 150000001875 compounds Chemical class 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 55
- 239000002121 nanofiber Substances 0.000 claims abstract description 31
- 229920002678 cellulose Polymers 0.000 claims abstract description 20
- 239000001913 cellulose Substances 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 13
- 238000000498 ball milling Methods 0.000 claims abstract description 10
- 239000011268 mixed slurry Substances 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 19
- 239000010457 zeolite Substances 0.000 claims description 18
- 239000002002 slurry Substances 0.000 claims description 17
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 14
- 229910021536 Zeolite Inorganic materials 0.000 claims description 13
- 239000012528 membrane Substances 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 11
- -1 polyethylene Polymers 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 239000004005 microsphere Substances 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 210000003850 cellular structure Anatomy 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000002070 nanowire Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 241000209094 Oryza Species 0.000 claims 2
- 235000007164 Oryza sativa Nutrition 0.000 claims 2
- 235000009566 rice Nutrition 0.000 claims 2
- 239000004411 aluminium Substances 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 230000001580 bacterial effect Effects 0.000 claims 1
- 238000009835 boiling Methods 0.000 claims 1
- 238000000227 grinding Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 230000018044 dehydration Effects 0.000 abstract 1
- 238000006297 dehydration reaction Methods 0.000 abstract 1
- 239000002585 base Substances 0.000 description 21
- 238000012360 testing method Methods 0.000 description 15
- 229920003043 Cellulose fiber Polymers 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 230000004888 barrier function Effects 0.000 description 10
- 235000011121 sodium hydroxide Nutrition 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- HTQOEHYNHFXMJJ-UHFFFAOYSA-N oxosilver zinc Chemical compound [Zn].[Ag]=O HTQOEHYNHFXMJJ-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 235000011194 food seasoning agent Nutrition 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- BSWGGJHLVUUXTL-UHFFFAOYSA-N silver zinc Chemical compound [Zn].[Ag] BSWGGJHLVUUXTL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920002749 Bacterial cellulose Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000005016 bacterial cellulose Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Cell Separators (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The present invention relates to microporous compound film and its preparation field, especially a kind of bacteria cellulose-base microporous compound film and its preparation method and application.The microporous compound film includes bacteria cellulose nanofiber and functional particles, its preparation step includes the purifying of bacteria cellulose nanofiber, bacteria cellulose nanofiber uniformly mixes in a solvent, under ball milling and ultrasonic wave added with functional particles, mixed slurry pre-dehydration in film forming grinding tool obtains wet film, wet film finally obtains bacteria cellulose-base microporous compound film of the invention by dry, roll-in.The advantages that microporous compound film of the invention has physics, stable chemical performance, and aperture size is adjustable, and pore-size distribution is narrow, has a good application prospect in lithium ion battery and alkaline battery.Of the invention preparation is simple, low in cost, environmental-friendly.
Description
Technical field
The present invention relates to microporous compound film and its preparation field, especially a kind of bacteria cellulose-base microporous compound film and its
Preparation method and application.
Background technique
With the fast development of New Energy Industry, power and energy-storage battery have obtained unprecedented concern.As battery
Key components, diaphragm has a major impact the security performance of battery, multiplying power discharging property and cycle performance.The kind of battery
Class is more, but classifies from configuration aspects, mainly includes microporous compound film and dense film two major classes, wherein lithium ion battery and big
The diaphragm that partial alkaline battery uses belongs to microporous compound film scope.
As the critical material of lithium ion battery, the lithium electric separator of current commodity is compound with polyethylene and polypropylene microporous
Based on film, but power lithium-ion battery field can not be applied to due to the limitation of membrane material nature.Currently, about power
The research of type lithium ion battery separator becomes hot spot, and it is urgent that the comprehensive high temperature safety for improving diaphragm and electric property become needs
It solves the problems, such as.
As high performance alkaline battery, such as the key component of zinc-silver oxide cell, the performance of diaphragm has become battery performance and mentions
The bottleneck risen.The problems such as now widely used cellulose acetate film is poor due to oxidative resistance has seriously restricted such electricity
The performance in pond plays, and the strong new types of diaphragm material of exploitation oxidative resistance, alkali resistance also becomes needs and urgently solves the problems, such as.
Bacterial cellulose wet-coating is led in view of the above-mentioned problems, application for a patent for invention (publication number CN104157815 A) uses
Cross solvent displacement, the method for hot pressing prepares lithium ion battery separator.But it is discovered by experiment that diaphragm prepared by this method
Porosity it is lower, aperture is smaller, and reason is easily occur adhesion in hot pressing between nanofiber, leads to the porous structure of film
It is destroyed.There is researcher's blended metal oxide in cellulose acetate, zinc-silver oxide cell diaphragm is prepared by solution film casting method, but
It is that diaphragm intensity prepared by this method is low, film resistance is larger, is also unable to satisfy strict demand of the heavy-duty battery to diaphragm.
It therefore meets the research accepting a heavy burden road for the electrochmical power source microporous compound film that the application fields such as power and energy storage require
Far, need from material of preparing and technique etc. carry out deeper into research.
Summary of the invention
The purpose of the present invention is to provide a kind of bacteria cellulose-base microporous compound films and its preparation method and application, use this
Method preparation microporous compound film have microfabricated tunable, temperature tolerance is good, ionic conductivity is high, reason/change stability is good, production work
The advantages that skill is simple, at low cost can meet the needs of large-scale industrial production.
The technical solution of the present invention is as follows:
A kind of bacteria cellulose-base microporous compound film, the microporous compound film include bacteria cellulose nanofiber and function grain
Son, wherein functional particles include organic functional particles or inorganic functional particle, bacteria cellulose nanofiber in microporous compound film
Mass ratio with functional particles is 1:0.01~1:20.
The diameter of the bacteria cellulose nanofiber is 10nm~1000nm, and draw ratio is 100~10000.
The functional particles play bridge formation function between nanofiber, prevent stick to each other between nanofiber, have and adjust
Save the effect of composite membrane cellular structure.
The organic functions particle includes poly (methyl methacrylate) micro-sphere, polyethylene microballoon, polypropylene microballoon, polyphenyl
Ethylene microballoon, Kynoar microballoon, polytetrafluoroethylene (PTFE) microballoon, the organic micro-spheres partial size range are 0.01~2.0 μm.
The inorganic functional particle includes metal oxide particle, ceramic particle or has a micro-pore composite structure, mesoporous
The zeolites nanoparticle of structure, metal oxide particle are iron oxide, zinc oxide, calcium oxide or magnesia, and ceramic particle is
Aluminium oxide, zirconium oxide, silica or titanium dioxide, the zeolites nanoparticle with micro-pore composite structure, meso-hole structure are
NaA zeolite, MFI zeolite, y-type zeolite, MCM-41 zeolite or MCM-48 zeolite, the functional particles particle size range be 0.01~
2.0μm。
The preparation method of the bacteria cellulose-base microporous compound film, includes the following steps:
(1) bacteria cellulose nanofiber is boiled in sodium hydroxide solution, centrifugal filtration obtains pure Nanowire
Dimension；
(2) nanofiber is mixed in a solvent with functional particles, and is uniformly mixed under ball milling and ultrasonic wave added, obtained
Mixed slurry；
(3) above-mentioned slurry is imported in film die, removes most of solvent in advance under vacuum aided；
(4) wet film obtains bacteria cellulose-base microporous compound film after vacuum drying, roll squeezer compacting.
The solid content of the mixed slurry is 0.5wt%~35wt%.
The film die be with 20 mesh~porous filter screens of 2000 mesh pore diameter ranges, the roughness of strainer is less than 10
μm。
The pre- removing major part solvent refers to 30wt%~95wt% of whole solvents in removing film.
The application of the bacteria cellulose-base microporous compound film, the microporous compound film are applied to lithium ion battery or alkalinity
In battery.
The invention has the advantages and beneficial effects that:
1, the method for the present invention includes the purifying of bacteria cellulose nanofiber, bacteria cellulose nanofiber and functional particles
It is mixed under ball milling and ultrasonic wave added, mixed slurry pre- desolventizing in film forming grinding tool obtains wet film, and wet film is by dry, roll-in
And etc., finally obtain bacteria cellulose-base microporous compound film of the invention.The bacteria cellulose obtained using the method for the present invention
Base microporous compound film, aperture<200nm, porosity>60%, percent thermal shrinkage<3% of 2h at 150 DEG C, be suitable for lithium electricity every
Film and alkaline battery separator.
2, the preparation method of bacteria cellulose-base microporous compound film of the present invention has simple for process, cost
The characteristics of cheap, environmental-friendly, process cycle is short, energy conservation and environmental protection, is suitble to large-scale production.
3, microporous compound film of the invention has physics, stable chemical performance, and aperture size is adjustable, and it is excellent that pore-size distribution is narrow etc.
Point has a good application prospect in lithium ion battery and alkaline battery.
Detailed description of the invention
Fig. 1 is the surface electron microscopic picture that the present invention prepares bacteria cellulose film by natural seasoning.
Fig. 2 is the surface electromicroscopic photograph of bacteria cellulose-base microporous compound film prepared by the present invention.
Specific embodiment
In a specific embodiment, bacteria cellulose-base microporous compound film of the present invention is by bacteria cellulose Nanowire
Dimension is mixed with a certain amount of functional particles (organic functions particle or inorganic functional particle), pre- desolventizing by vacuum aided,
Complete desolventizing, roll-in and etc. after obtain.
Wherein, the diameter of bacteria cellulose nanofiber is 10nm~1000nm (preferred scope is 50nm~300nm), long
Diameter ratio is 100~10000 (preferred scope is 200~1000).The functional particles play bridge formation function between nanofiber,
Adhesion between nanofiber is prevented, has the function of adjusting composite membrane cellular structure.Organic functions particle includes polymethylacrylic acid
Methyl esters microballoon, polyethylene microballoon, polypropylene microballoon, polystyrene microsphere, Kynoar microballoon or polytetrafluoroethylene (PTFE) microballoon etc.
Organic micro-spheres, organic micro-spheres partial size range are 0.01~2.0 μm (preferred scope is 0.03 μm~1.0 μm).Inorganic functional particle
Include: metal oxide particle (such as: iron oxide, zinc oxide, calcium oxide or magnesia), ceramic particle (such as: aluminium oxide, oxidation
Zirconium, silica, titanium dioxide), and (such as: NaA boils the zeolites nanoparticle with micro-pore composite structure, meso-hole structure
Stone, MFI zeolite, y-type zeolite, MCM-41 zeolite, MCM-48 zeolite) etc., inorganic functional particle diameter range is 0.01~2.0 μm
(preferred scope is 0.05 μm~1.0 μm).
The preparation method of bacteria cellulose-base microporous compound film of the present invention comprising the steps of:
(1) bacteria cellulose nanofiber is boiled certain time (20~180 minutes) in sodium hydroxide solution, is centrifuged
Filtering obtains pure nanofiber；
(2) nanofiber is uniformly mixed in a solvent, under ball milling and ultrasonic wave added with functional particles, obtains mixing slurry
Material；
(3) above-mentioned slurry is imported in film die, removes most of solvent in advance under vacuum aided；
(4) wet film is vacuum dried, obtains certain thickness bacteria cellulose-base microporous compound film after roll squeezer compacting.Its
In, the thickness range of microporous compound film is 15 μm~60 μm, and average pore size scope is 50nm~300nm, and porosity ranges are
45%~80%；Transverse tensile strength range is 15~35MPa, and longitudinal tensile strength range is 18~35MPa.
In step (2), the solvent includes water, methanol, ethyl alcohol, acetone, tetrahydrofuran, dimethylformamide or diformazan
Yl acetamide equal solvent, the solid content of the mixed slurry are 0.5wt%~35wt%.In step (3), the film forming mould
Tool is the porous filter screen with 0.02 μm~100 μm (preferred scope is 0.5 μm~50 μm) pore diameter ranges, and the roughness of strainer is small
In 10 μm.In step (4), the pre- removing major part solvent refers to 30wt%~95wt% of whole solvents in removing film.
In the following, being further elaborated on by embodiment and attached drawing to the present invention.
Embodiment 1
By 20 grams of diameters be about 60nm, the bacteria cellulose fibre that draw ratio is 300 is added to 500ml mass concentration and is
It in 20% sodium hydrate aqueous solution, is handled 90 minutes at 80 DEG C, is centrifuged repeatedly washing until nanofiber is neutrality.By 10 grams
Purified bacteria cellulose fibre mixes in water with the Zirconia particles that 1.5 gram particle diameters are 50nm, auxiliary in ball milling and ultrasound
Help the lower uniform slurry of acquisition, solid content 18wt%.Above-mentioned slurry is poured into the film forming grinding tool with 800 mesh apertures, true
Reciprocal of duty cycle is to remove moisture in advance under 0.8 atmospheric pressure.Above-mentioned wet film is dried into 4h at 100 DEG C, finally obtains bacterium by roll-in
Cellulose base microporous barrier.
Above-mentioned microporous barrier is tested according to prior art preparation at lithium-ion button battery.
Membrane structure test result: 25 μm of thickness, average pore size 120nm, porosity 63%.
Film-strength test result: transverse tensile strength 25MPa, longitudinal tensile strength 24MPa.
Battery punctures test result: standing 30min after fully charged, battery is pierced through with nail, without phenomenon on fire.
Battery high rate performance test result: 25% when the discharge capacity of battery is 0.2C multiplying power under 32C.
Embodiment 2
By 20 grams of diameters be about 100nm, the bacteria cellulose fibre that draw ratio is 1000 is added to 500ml mass concentration and is
It in 40% sodium hydrate aqueous solution, is handled 60 minutes at 100 DEG C, is centrifuged repeatedly washing until nanofiber is neutrality.By 10
Gram purified bacteria cellulose fibre mixes in acetone with the polytetrafluoroethylparticle particle that 2.5 gram particle diameters are 100nm, in ball milling
With obtain uniform slurry under ultrasonic wave added, slurry solid content is 5wt%.Above-mentioned slurry is poured into the film forming with 1200 mesh apertures
In grinding tool, moisture is removed in advance in the case where vacuum degree is 1.0 atmospheric pressure.Above-mentioned wet film is dried into 4h at 100 DEG C, finally passes through roller
Pressure obtains bacteria cellulose-base microporous barrier.
Above-mentioned microporous barrier is tested according to prior art preparation at zinc-silver button cell.
Membrane structure test result: 35 μm of thickness, average pore size 90nm, porosity 60%.
Film-strength test result: transverse tensile strength 19MPa, longitudinal tensile strength 21MPa.
Battery punctures test result: standing 30min after fully charged, battery is pierced through with nail, without phenomenon on fire.
Battery high rate performance test result: 38% when the discharge capacity of battery is 0.2C multiplying power under 10C.
Embodiment 3
By 20 grams of diameters be about 200nm, the bacteria cellulose fibre that draw ratio is 500 is added to 500ml mass concentration and is
It in 10% sodium hydrate aqueous solution, is handled 120 minutes at 100 DEG C, is centrifuged repeatedly washing until nanofiber is neutrality.By 10
Gram purified bacteria cellulose fibre mixes in dimethylformamide with the MFI zeolite particles that 1.0 gram particle diameters are 200nm,
Uniform slurry is obtained under ball milling and ultrasonic wave added, slurry solid content is 25wt%.Above-mentioned slurry is poured into 300 mesh apertures
Film forming grinding tool in, vacuum degree be 0.6 atmospheric pressure under remove moisture in advance.Above-mentioned wet film is dried into 4h at 100 DEG C, finally
Bacteria cellulose-base microporous barrier is obtained by roll-in.
Above-mentioned microporous barrier is tested according to prior art preparation at lithium-ion button battery.
Membrane structure test result: 30 μm of thickness, average pore size 150nm, porosity 67%.
Film-strength test result: transverse tensile strength 24MPa, longitudinal tensile strength 22MPa.
Battery punctures test result: standing 30min after fully charged, battery is pierced through with nail, without phenomenon on fire.
Battery high rate performance test result: 28% when the discharge capacity of battery is 0.2C multiplying power under 32C.
Embodiment 4
By 20 grams of diameters be about 60nm, the bacteria cellulose fibre that draw ratio is 6000 is added to 500ml mass concentration and is
It in 20% sodium hydrate aqueous solution, is handled 90 minutes at 100 DEG C, is centrifuged repeatedly washing until nanofiber is neutrality.By 10
Gram purified bacteria cellulose fibre mixes in methyl alcohol with the Kynoar particle that 2.0 gram particle diameters are 200nm, in ball milling
With obtain uniform slurry under ultrasonic wave added, slurry solid content is 30wt%.Above-mentioned slurry is poured into the film forming with 600 mesh apertures
In grinding tool, moisture is removed in advance in the case where vacuum degree is 0.8 atmospheric pressure.Above-mentioned wet film is dried into 4h at 100 DEG C, finally passes through roller
Pressure obtains bacteria cellulose-base microporous barrier.
Above-mentioned microporous barrier is tested according to prior art preparation at zinc-silver button cell.
Membrane structure test result: 40 μm of thickness, average pore size 80nm, porosity 55%.
Film-strength test result: transverse tensile strength 22MPa, longitudinal tensile strength 23MPa.
Battery punctures test result: standing 30min after fully charged, battery is pierced through with nail, without phenomenon on fire.
Battery high rate performance test result: 50% when the discharge capacity of battery is 1.0C under 20C.
Embodiment 5
It is about 60nm by 20 grams of diameters, the bacteria cellulose fibre that draw ratio is 800 adds 20 grams of bacteria cellulose dry powder
Enter to 500ml mass concentration be 20% sodium hydrate aqueous solution in, handle 120 minutes at 90 DEG C, be centrifuged repeatedly washing up to
Nanofiber is neutrality.The magnesia particle that 10 grams of purified bacteria cellulose fibres and 3.2 gram particle diameters are 1000nm is existed
It is mixed in ethyl alcohol, uniform slurry is obtained under ball milling and ultrasonic wave added.Above-mentioned slurry is poured into the mill of the film forming with 100 mesh apertures
In tool, moisture is removed in advance in the case where vacuum degree is 0.2 atmospheric pressure.Above-mentioned wet film is dried into 4h at 100 DEG C, finally passes through roll-in
Obtain bacteria cellulose-base microporous barrier.
Above-mentioned microporous barrier is tested according to prior art preparation at lithium-ion button battery.
Membrane structure test result: 26 μm of thickness, average pore size 200nm, porosity 58%.
Film-strength test result: transverse tensile strength 20MPa, longitudinal tensile strength 20MPa.
Battery punctures test result: standing 30min after fully charged, battery is pierced through with nail, without phenomenon on fire.
Battery high rate performance test result: 19% when the discharge capacity of battery is 0.2C multiplying power under 32C.
As shown in Figure 1, can be seen that the film from the surface electron microscopic picture for preparing bacteria cellulose film by natural seasoning
Surface duct it is less, close adhesion between most of cellulose fibre causes the structure of film finer and close, it is normal to be unfavorable for battery
Work.
As shown in Fig. 2, it is multiple to can be seen that this from the surface electromicroscopic photograph of prepared bacteria cellulose-base microporous compound film
It closes film surface and is distributed a large amount of functional particles, it can be found that bacteria cellulose fibre, good with functional particles between functional particles
Good fusion effectively prevent adhesion between fiber, assigns the good lyophily of composite membrane and heat resistance, is conducive to battery charging and discharging.
Embodiment the result shows that, bacteria cellulose-base microporous compound film provided by the invention and preparation method thereof, due to will
Absorbency and heat-resist nanofiber and functional particle are compound through row, overcome the easy adhesion of nanofiber, the densification that forms a film,
The low problem of porosity realizes the raising of battery diaphragm comprehensive performance, and prepared lithium ion battery is in heat resistance, multiplying power
Multiplying power discharging property of performance and zinc-silver oxide cell etc. is better than battery, and the simple, cost with composite membrane preparation process
Low advantage, without expensive production equipment, easy to operate, high production efficiency is, it can be achieved that large-scale industrial production.
Claims (6)
1. a kind of bacteria cellulose-base microporous compound film, which is characterized in that the microporous compound film includes bacteria cellulose Nanowire
Peacekeeping functional particles, wherein functional particles include organic functional particles or inorganic functional particle, bacterial fibers in microporous compound film
The mass ratio of plain nanofiber and functional particles is 1:0.01~1:20；
The organic functions particle includes poly (methyl methacrylate) micro-sphere, polyethylene microballoon, polypropylene microballoon, polystyrene
Microballoon, Kynoar microballoon or polytetrafluoroethylene (PTFE) microballoon, the organic functions particle diameter range are 0.01~2.0 μm；
The inorganic functional particle include metal oxide particle, ceramic particle or have micro-pore composite structure, meso-hole structure
Zeolites nanoparticle, metal oxide particle be iron oxide, zinc oxide, calcium oxide or magnesia, ceramic particle be oxidation
Aluminium, zirconium oxide, silica or titanium dioxide, the zeolites nanoparticle with micro-pore composite structure, meso-hole structure are NaA boiling
Stone, MFI zeolite, y-type zeolite, MCM-41 zeolite or MCM-48 zeolite, the inorganic functional particle diameter range be 0.01~
2.0μm；
The preparation method of the bacteria cellulose-base microporous compound film, includes the following steps:
(1) bacteria cellulose nanofiber is boiled in sodium hydroxide solution, centrifugal filtration obtains pure nanofiber；
(2) nanofiber is mixed in a solvent with functional particles, and is uniformly mixed under ball milling and ultrasonic wave added, mixed
Slurry；
(3) above-mentioned slurry is imported in film die, removed in advance under vacuum aided in film the 30wt% of whole solvents~
95wt%；
(4) wet film obtains bacteria cellulose-base microporous compound film after vacuum drying, roll squeezer compacting.
2. bacteria cellulose-base microporous compound film described in accordance with the claim 1, which is characterized in that the bacteria cellulose is received
The diameter of rice fiber is 10nm~1000nm, and draw ratio is 100~10000.
3. bacteria cellulose-base microporous compound film described in accordance with the claim 1, which is characterized in that the functional particles are being received
Bridge formation function is played between rice fiber, prevents stick to each other between nanofiber, has the function of adjusting composite membrane cellular structure.
4. bacteria cellulose-base microporous compound film described in accordance with the claim 1, which is characterized in that the mixed slurry is consolidated
Content is 0.5wt%~35wt%.
5. bacteria cellulose-base microporous compound film according to claim 1, it is characterised in that: the film die is tool
There is 20 mesh~2000 mesh pore diameter ranges porous filter screen, the roughness of strainer is less than 10 μm.
6. the application of bacteria cellulose-base microporous compound film described in a kind of one of claim 1 to 5, which is characterized in that this is micro-
Hole composite membrane is applied in lithium ion battery or alkaline battery.
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| CN106654122A (en) * | 2017-01-18 | 2017-05-10 | 山东纳美德生物科技有限公司 | Preparation method of power lithium ion battery diaphragm |
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| CN108134035A (en) * | 2017-11-07 | 2018-06-08 | 深圳市晶特智造科技有限公司 | A kind of micropore complex lithium electric separator and preparation method thereof |
| CN109037561A (en) * | 2018-08-02 | 2018-12-18 | 佛山腾鲤新能源科技有限公司 | A kind of high temp resistance lithium ion cell diaphragm |
| KR102353062B1 (en) | 2018-09-03 | 2022-01-19 | 주식회사 엘지에너지솔루션 | Separator for Secondary Battery without Separator Base Member |
| CN112201905A (en) * | 2020-11-09 | 2021-01-08 | 中山市世豹新能源有限公司 | Cellulose-based lithium battery flame-retardant diaphragm and preparation method thereof |
| CN113036194B (en) * | 2021-03-09 | 2022-06-07 | 湖北工程学院 | Preparation method of organic-inorganic composite alkaline polyelectrolyte membrane |
| KR20240089369A (en) * | 2021-10-21 | 2024-06-20 | 베이징 유청 테크놀로지 씨오., 엘티디. | Modified composite separator and method for manufacturing the same |
| CN114050372A (en) * | 2021-10-26 | 2022-02-15 | 惠州锂威新能源科技有限公司 | Diaphragm for lithium ion battery and preparation method and application thereof |
| CN114256560A (en) * | 2021-11-24 | 2022-03-29 | 中国科学院宁波材料技术与工程研究所 | Cellulose inorganic composite membrane, high-temperature-resistant battery diaphragm, and preparation method and application thereof |
| CN115036646A (en) * | 2022-04-26 | 2022-09-09 | 青岛科技大学 | Nano composite material battery diaphragm, preparation method thereof and lithium battery |
| CN115652698A (en) * | 2022-11-24 | 2023-01-31 | 闽江学院 | Method for preparing high-strength flame-retardant organic-inorganic nano hybrid fiber membrane by one-pot method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102522517A (en) * | 2011-12-22 | 2012-06-27 | 中国科学院青岛生物能源与过程研究所 | Cellulose/inorganic particle composite diaphragm for lithium secondary battery and preparation method thereof |
| CN103078077A (en) * | 2013-01-17 | 2013-05-01 | 中国科学院金属研究所 | Lithium ion battery diaphragm with special structure and preparation method thereof |
| CN104157815A (en) * | 2014-08-22 | 2014-11-19 | 海南光宇生物科技有限公司 | Bacterial cellulose porous thin film and preparation method thereof |
-
2015
- 2015-05-26 CN CN201510272604.6A patent/CN106299213B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102522517A (en) * | 2011-12-22 | 2012-06-27 | 中国科学院青岛生物能源与过程研究所 | Cellulose/inorganic particle composite diaphragm for lithium secondary battery and preparation method thereof |
| CN103078077A (en) * | 2013-01-17 | 2013-05-01 | 中国科学院金属研究所 | Lithium ion battery diaphragm with special structure and preparation method thereof |
| CN104157815A (en) * | 2014-08-22 | 2014-11-19 | 海南光宇生物科技有限公司 | Bacterial cellulose porous thin film and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Bacterial cellulose nanofibrous membrane as thermal stable separator for lithium-ion batteries;Fengjing Jiang等;《Journal of Power Sources》;20141222;第279卷;第21-27页 * |
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